Nitroglucoside explosive



Patented May 31, 1927.

TES

mam

ROBERT C. MORAN, OF WOODBURY, NEW JERSEY, ASSIGNOR TO E. I. DU PONT DE NEMOURS & COMPANY, OF WILMINGTON, DELAWARE, A CORPORATION OF DELA- WARE,

No Drawing. Original application filed January 23, 1923, Serial No. 614,455. Divided and this application filed November 6, 1925. Serial No. 67,208.

This invention relates to explosives, and particularly to high explosives such as dynamite, and comprises explosives of this type I which contain, as the main explosive constituent or explosive base, a nitrated glucoside of a glycol either alone or in conjunction with a nitrated polyhydric alcohol.

The term glucoside is used herein in a generic sense to refer to the ethers formed by the condensation of hydroxy-hydrocarbons, and particularly glycols, with sugars (aldo-sugars) such as dextrose, mannosc, alactose, andother hexoses, rhamnose (a methyl-pentose), and various other sugars.

These glucosides are characterized by yieldmg upon hydrolysis a sugar and a glycol. In the following description the chemical constitution of specific glucosides will be incheated by reference to both the sugar and the glycol components fromwhich the particular glucoside maybe assumed to have been derived. Thus, I designate the glucoside obtainable by the interaction of dextrose and ethylene glycol as the dextroseglucoside of ethylene glycol, the generally accepted structural formula of the glucoside be1ng:

As set out in, co-periding application Serial No. 614,455, filed January 23, 1923, of which this application is a division, nitrated sugars have heretofore been used in the production of explosives for commercial purposes. The use of nitrated sugars possesses on the one hand the following advantages: first, it makes possible cheaper explosive bases due to the replacement in part of the nitratedpolyhydric alcohols by .the cheaper nitrated sugar; and, second, it permits the preparation of low-freezing explosive bases through the admixture of nitrated sugars with the nitrated polyhydric alcohols. On the other hand, the very great objection to the use of nitrated sugars in commercial explosives has been their instability.

For the production of explosives of lowfreezing property, nitrated polymerized glycerine has been found advantageous. ,Such explosives are stable, but have the objection of relatively high cost, since nitrated polymerized glycerine is even more expensive than nitroglycerine or ethylene dinitratey' I have now discovered that nitrated g'hicd sides of the glycols may be used as explosives with essentially all the above-cited advantages associated with the use of. both nitrated sugars and nitrated' polymerized glycerine and at the same time without the ond, a stable explosive base with nitrated polyhydric alcohol is obtained; and, third, an explosive base with the nitrated polyhydrie alcohol can be obtained having a .degree of low-freezing property comparable to that imparted by nitrated polymerized glycerine, and at a decided saving.

The glucosides, such as the dextrose, mannose, eta, glucosides of tlie glycols, such as ethylene glycol, propylene glycol, butylene glycol, trimethylene glycol,-etc., may be prepared by methods described in the literature (Ber. 26, 2411; 27, 2483; 28, 1145).

Nitrated glucosides of the glycols'may be prepared from the corresponding glucosides by the general method described in the literature (Ber. 31, 68). For use according to my invention such nitrated glucosides, as for example the nitrated dextrose-glucoside of ethylene glycol, may be mixed with a nitrated polyhydric alcohol, as for example nitrated ethylene glycol, in proportions ranging from 80% to 20% nitrated dextroseglucoside of ethylene glycol to from 20% to 80% of nitrated ethylene glycol. While I have mentioned the above range of proportions of the nitrates as suitable, I Wish it to be understood that I do not limit myself to any specific proportions.

Instead of mixing, as such, the nitrated glucosides of glycols and nitrated polyhydric alcohols, I prefer to nitrate the corresponding mixtures of the glucosides of glycols with polyhydric alcohols, as for example, a mixture of dextrose-glucoside of ethylene glycol and ethylene glycol. This operation may be performed as follows:

Thirty parts of a glucoside, such as the dextrose-glucoside of ethylene glycol, aredissolved in 7 0 parts of a polyhydric alcohol such as ethylene glycol, and one part of this mixture is nitrated with 5 parts of a mixed acid of the approximate composition: Sulfuric acid 56%, nitric acid 44%. The temperature and time of nitration are approximately the same as for the glycol alone. When the nitration is complete, the solution or mixture of ethylene dinitrate and nitrated glucoside of ethylene glycol is separated from the spent acid and stirred until neutral with a 6% solution of sodium carbonate, in water, at a temperature of aboutg7 0-100 F. Instead of sodium carbonate another alkali such as sodium hydroxide, as well as sodium bicarbonate, may be used. The alkali solution is then drawn off and the nitrated mix ture is washed with pure water at a temperature of 7 O100 F. The mixture of ethylene dinitrate and nitrated glucoside is then pure, and ready for use.

In regard to the above proportions, temperatures, etc., all these may be Varied just as they can in the manufacture of nitroglycerine. The mixed acid can be of various strengths, either anhydrous or containing up to several per cent (4 or 5%) of water. Different proportions of glycol, glucoside and mixed acid, different neutralizing agents of varying strength, and difi'erent temperatures of treatment are possible.

The same mixture proportions, nitration conditions, etc., hold for the other representative mixtures of a glucosideof a glycol and a polyhydric alcohol such as, for instance, a mixture of the/glucoside of ethylene glycol and glycerine.

According to my invention, desirable forms of dynamite may be made from explosive bases containing nitrated glucosides, as, for example, the nitrated dextrose-glucoside of ethylene glycol, by mixing such base with the usualingredients which make up nitroglycerine dynamites, such, for example, as sodium or potassium or ammonium nitrate, wood meal, etc. Moreover, it is possible by 'verted into a nitrate Ammo- Dyna- 3 223 nia mite. Igite dyna mite.

Per cent. Per cent. Per cent. Explosive base 40 33 10 Nitrocotton h k Absorbent 14 The explosive base in the above examples may consist wholly of the nitrated glucoside of a glycol, such as, for instance, the nitrated dextrose-glucoside of butylene glycol, or the nitrated mannose-glucoside of ethylene glycol. Or the explosive base in the above dynamite formulas may be composed of a mixture of one of the nit-rated gluc-osides of glycol With one of the nitrated polyhydric alcohols, such as, ethylene, propylene, and butylene, dinitrates, trinitroglycerine, and nitrated polymerized glycerine. Suitable proportions of the two ingredients may be used such as equal parts of nitrated glucoside and nitrated alcohol, or instead of equal parts of the two constituents, the explosive base may consist, for example, of 30 parts nitrated glucoside to 7 0 parts nitrated polyhydric alcohol.

The nitrated glucosides which I prefer to use are derived from glucosides obtainable by condensing aldo-hexoses 'With glycols having from 2 to 9 carbon atoms, thus including such glycols as ethylene, butylene, and hexylene, glycols.

For the production of gelatin dynamitcs the nitrated glucoside-glycol mixtures, are especially valuable, such mixtures gelatinizing more readily with nitrocotton than either nitrated sugar-glycol mixtures or nitrated polymerized glycerine. As examples of such nitrated glucoside-glycol mixtures there may be mentioned the'mix tures of ethylene dinitrate with the dextrose-glucoside of ethylene glycol or of trim'ethylene glycol. A By the expressions nitrated glucosides and nitrated polyhydric alcohols I mean, in general, glucosides and polyhydric alcohols which are completely nitrated, that is, in which each hydroxyl group has been con- (O-'-NO grou Partially nit-rated glucosides and alcoho s, however, also come within the scope'of my invention. e

In the nitration of the glucoside, one or no I more of the hydroxyl groups may be converted to nitric esters, depending upon the amount of nitrating acid used. The end product, when the nitration is carried to While the penta-nitric ester is given as a specific example, it is understood that the extent of the nitration may be varied, as

' has been pointed out.

While'I have described my new explosive compositions in detail, it will be understood that many changes may be made therein without departing from the spirit or scope of my invention.

' I claim:

1. An' explosive mixture comprising a nitrated glucoside of a glycol.

2. An explosive mixture comprising a nitrated glucoside of a glycol having from 2 to 9 carbon atoms.

3. A dynamite containing a nitrated dexe trose-glucoside of a glycol.

4. A dynamlte containing the nitrated dextrose-glucoside oi ethylene glycol.

5. An explosive composition containing a nitrated dextroselucoside of a glycol and a nitrated polyhy ric alcohol.

6. An ex losive composition containing the nitrate dextrose-glucoside of ethylene. glycol and a nitrated .polyhydric alcohol.

7. An explosive composition containing the nitrated dextrose-glucoside ofethylene glycol and ,nitrated ethylene glycol.

8. An explosive composition comprising a nitrated glucoside of a glycol and an alkylenedi'nitrate. P

9. A dynamite comprising a nitrated aldo-hexose-glucoside of a glycol.

10. A dynamlte containing as the P 5 in completion, is the penta-nitric ester of the dextrose glucoside of ethylene glycol; the probable structural formula of which is 14. An explosivecomposition comprising a nitrated hexose-glucoside of a glycol and an alkylene dinitrate. v

'15. An explosive composition comprising a nitrated hexose-glucoside of ethylene glycol and nitrated ethylene glycol.

16.-An ex losive-composition comprising a nitrated g ucoside of a glycol and nitroglycerine.

17. An explosive composition comprising a. nitrated glucoside of ethylene glycol and nitroglycerine.

18. An explosive mixture comprising a nitrated glucoside of ethylene glycol.

I 19. An explosive composition comprising "a nitrated glucoside of ethylene glycol and 'nitrated ethylene glycol.

In testimony whereof I aflix my signature.

ROBERT o; MORAN. 

